DE3825671A1 - Process for producing panes having a high transmission behaviour in the visible spectral region and a high reflection behaviour for heat radiation, and panes produced by the process - Google Patents

Process for producing panes having a high transmission behaviour in the visible spectral region and a high reflection behaviour for heat radiation, and panes produced by the process

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Publication number
DE3825671A1
DE3825671A1 DE3825671A DE3825671A DE3825671A1 DE 3825671 A1 DE3825671 A1 DE 3825671A1 DE 3825671 A DE3825671 A DE 3825671A DE 3825671 A DE3825671 A DE 3825671A DE 3825671 A1 DE3825671 A1 DE 3825671A1
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Germany
Prior art keywords
layer
oxide
weight
silver
alloy
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Withdrawn
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DE3825671A
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German (de)
Inventor
Joachim Dr Szczyrbowski
Anton Dr Dietrich
Klaus Dr Hartig
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Leybold AG
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Leybold AG
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Publication date
Priority to DE3726488 priority Critical
Application filed by Leybold AG filed Critical Leybold AG
Priority to DE3825671A priority patent/DE3825671A1/en
Publication of DE3825671A1 publication Critical patent/DE3825671A1/en
Application status is Withdrawn legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3618Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10009Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheet
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10165Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin particular functional features of the laminated glazing
    • B32B17/10174Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10165Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin particular functional features of the laminated glazing
    • B32B17/10174Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • B32B17/1022Metallic coatings
    • B32B17/10229Metallic layers sandwiched by dielectric layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/1055Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin characterized by the resin layer, i.e. interlayer
    • B32B17/10761Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3644Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3652Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the coating stack containing at least one sacrificial layer to protect the metal from oxidation
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3657Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
    • C03C17/366Low-emissivity or solar control coatings
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3681Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating being used in glazing, e.g. windows or windscreens
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60JWINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00Windows; Windscreens; Accessories therefor
    • B60J1/002Windows; Windscreens; Accessories therefor with means for clear vision, e.g. anti-frost or defog panes, rain shields

Abstract

A process for producing panes having a high transmission behaviour in the visible spectral region and a high reflection behaviour for heat radiation as well as low surface resistivity. A layer system is built up in the following order on substrates of mineral glass: Layer 1: oxide from the group comprising tin oxide, silica, alumina, tantalum oxide and zirconium oxide or mixed oxides thereof. Layer 2: alloy of 80 per cent by weight of nickel and 20 per cent by weight of chromium Layer 3: silver or a silver alloy with a silver content of at least 50 per cent by weight Layer 4: alloy of 80 per cent by weight of nickel and 20 per cent by weight of chromium Layer 5: oxide from the group comprising tin oxide, silica, alumina, tantalum oxide and zirconium oxide or mixed oxides thereof. Subsequently, the substrate is heated together with the complete layer pack to the softening temperature of the glass and bent into the final shape. <IMAGE>

Description

Die Erfindung betrifft ein Verfahren zum Herstellen von Scheiben mit hohem Transmissionsverhalten im sichtbaren Spektralbereich und mit hohem Reflexionsverhalten für Wärmestrahlung und niedrigem Flächenwiderstand nach dem Oberbegriff des Patentanspruchs 8. The invention relates to a method for producing discs having a high transmittance in the visible spectrum and with high reflection characteristics for thermal radiation and low sheet resistance according to the preamble of patent claim 8.

Derartige Scheiben sollen einen möglichst großen Anteil des sichtbaren Lichts durchlassen und einen möglichst großen Anteil des nichtsichtbaren spektralen Anteils der Sonnenstrahlung zurückhalten. Such sheets are to transmit the largest possible amount of visible light and retain as large a proportion of the non-visible spectral component of solar radiation. Diese Maßnahme soll im Sommer verhindern, daß die unerwünschte Wärmestrahlung des Sonnenlichts in Räume eindringt. This is to prevent the summer that the unwanted heat radiation from sunlight penetrates into spaces. Besonders bei Kraftfahrzeugen ist dieser Effekt wegen der schrägge stellten und dadurch sehr großen Front- und Heckscheiben besonders unerwünscht. Particularly in motor vehicles, this effect is presented because of schrägge and thus very large front and rear windows particularly undesirable.

Durch die DE-OS 33 07 661 und die EP-OS 1 04 870 ist es bekannt, eine Silberschicht und eine unmittelbar auf das Silber aufgebrachte sehr dünne Metallschicht zwischen zwei Oxidschichten einzuschließen, wobei die dünne Metallschicht die Silberschicht gegen einen chemisch thermischen Angriff beim Herstellen der obersten Oxid schicht schützt. DE-OS 33 07 661 and EP-A 1 04 870 it is known to include a silver layer and a coating applied directly to the silver very thin metal layer between two oxide layers, wherein the thin metal layer, the silver layer against a chemically thermal attack in the manufacture the top oxide layer protects. Setzt man ein derartiges Schichtsystem jedoch Temperaturen oberhalb 150°C aus, so erfolgt eine Diffusion des Silbers in die angrenzende Oxid- und/oder Metallschicht, wobei ein starker Anstieg des Flächen widerstandes und eine entsprechende Verringerung der Transmissionswerte des Schichtsystems zu beobachten ist, dh zwei der wesentlichen Eigenschaften des Schicht systems werden verschlechtert. However, Substituting such a layer system temperatures above 150 ° C, so diffusion of the silver is carried in the adjoining oxide and / or metal layer with a strong increase of the junction resistance and a corresponding reduction of the transmission values ​​of the layer system is observed, ie two of the essential properties of the layer system are deteriorated.

Durch die EP-PS 35 906 ist es bekannt, auf einer Seite oder beiden Seiten einer Silberschicht eine dünne metal lische Schicht anzuordnen und dieses Schichtsystem gleichfalls zwischen zwei Oxidschichten einzubetten. By the EP-PS 35 906 it is known to arrange on one side or both sides of a layer of silver, a thin metallic layer and to embed this layer system equally between two oxide layers. Durch die dünne metallische Schicht soll eine größere Langzeitstabilität erreicht werden, wobei sich die Untersuchungen jedoch auf einen Temperaturbereich bis 120°C beschränken. The thin metallic layer has a greater long-term stability is to be achieved, with the studies, however, limited to a temperature range up to 120 ° C. Da weiterhin durch das Absorptions verhalten der metallischen Schichten eine Verschlechte rung der optischen Transparenz der beschichteten Sub strate eintritt, ist die Gesamtdicke der metallischen Schichten zur Erzielung eines bestinmten Transmissions verhaltens begrenzt, und es soll daher bevorzugt nur eine einzige metallische Schicht auf der dem Substrat abge wandten Seite der Silberschicht angebracht werden, damit die Verschlechterung der Transmissionswerte in Grenzen gehalten werden kann. Furthermore, since by the absorption of the metallic layers behave a Verschlechte tion of the optical transparency of the coated sub enters strate, the total thickness of the metal layers to achieve a bestinmten transmission behavior limited and it is therefore preferably only one metallic layer on the abge the substrate facing side of the silver layer are installed so that the deterioration of the transmission values ​​can be kept within limits. Es hat sich jedoch bei Verwendung von Substraten aus Mineralglas und einem derartigen Schichtsystem gezeigt, daß bei einer Erwärmung auf Temperaturen merklich oberhalb 150°C gleichfalls eine Verschlechterung der Schichteigenschaften eintrat, und zwar nicht nur durch eine an sich wünschenswerte Erhöhung der Transmissionswerte im sichtbaren Bereich, sondern gleichzeitig auch durch einen unerwünschten Anstieg des Flächenwiderstandes, so daß die Bordspannung eines normalen Kraftfahrzeuges nicht mehr ausreicht, um im Winter eine ausreichende Beheizung durchzuführen. However, it has been found in use of substrates made of mineral glass, and such a layer system that at a heating above 150 ° C also entered to temperatures significantly deterioration of the layer properties, and not only by a desirable per se increase the transmittance values ​​in the visible range, but so that the on-board voltage of a normal motor vehicle is no longer sufficient at the same time also an undesirable increase of the surface resistance, to perform an adequate heating in winter. Weiter hin wurden Flecken und unerwünschte Lichtstreuungen beobachtet, die offensichtlich auf eine teilweise Agglo meratbildung sowie auf eine teilweise Diffusion des Silbers in die Oxidschichten hinein zurückzuführen ist. Farther spots and undesirable light scattering were observed, which is apparently due to a partial Agglo meratbildung as well as for a partial diffusion of the silver in the oxide layers inside.

Dieses Verhalten läßt nur den Schluß zu, daß die Dicke der metallischen Schicht bzw. Schichten im Hinblick auf die angestrebten hohen Transmissionswerte im sichtbaren Bereich, die teilweise auf gesetzlichen Vorschriften zurückzuführen sind (Kraftfahrzeugscheiben), für einen wirksamen Schutz der Silberschicht, inbesondere bei höheren Temperaturen, nicht mehr ausreichend ist. This behavior only permits the conclusion that the thickness of the metallic layer or layers in view of the desired high transmittance values ​​in the visible range, which are partly due to legal requirements (vehicle wheels) higher for the effective protection of the silver layer, particularly at temperatures is no longer sufficient.

Es ist auch bekannt, gekrümmte oder gewölbte Scheiben mit annähernd ähnlichem spektralen Verhalten dadurch herzu stellen, daß man eine in andere Schichten eingebettete Silberschicht auf bereits verformte Glassubstrate auf bringt. It is also known to provide curved or domed disks, approximately similar spectral behavior near, characterized by bringing an embedded into other layers of the silver layer on already deformed glass substrates. Dies setzt jedoch spezielle Beschichtungsanlagen voraus, die der unterschiedlichen Formgebung der Substra te Rechnung tragen und durch komplizierte Blendenanord nungen die Einflüsse unterschiedlicher Abstände von Flächenelementen des Substrats von den Beschichtungs quellen und unterschiedlicher Auftreffwinkel des Schicht materials kompensieren. However, this requires special coating equipment requires carrying te of the different shape of the bill and Substra by complicated Blendenanord the influences of different distances from surface elements of the substrate voltages of the sources of coating and compensate for different incident angle of the layer materials.

Schließlich lassen sich mit einem Verfahren nach einer älteren Pastentanmeldung (P 35 43 178.4) Substrate aus Mineralglas mittels eines Vakuumbeschichtungsverfahrens mit einem fünfschichtigen System versehen, wodurch der Scheibe ein hohes Reflexionsverhalten für Wärmestrahlung bei gleichzeitig hohem Transmissionsverhalten für sicht bares Licht verliehen wird. Finally blank with a method according to an older Pastentanmeldung (P 35 43 178.4) provide substrates made of mineral glass by a vacuum coating method with a five-layer system, whereby the disc has a high reflection characteristics for thermal radiation while maintaining a high transmission characteristics for visible bares light is imparted. Das aufgebrachte Schicht system ist dabei so gewählt, daß die zunächst flache, beschichtete Scheibe einem Biegeprozeß unterzogen werden kann, bei dem die Erweichungstemperatur des Glases von ca. 650°C erreicht wird, ohne die Eigenschaften der beschichteten Scheibe im negativen Sinne zu verändern. The applied coating system is selected so that the initially flat, coated glass can be subjected to a bending process in which the softening temperature of the glass is achieved of about 650 ° C without changing the properties of the coated pane in a negative sense. Die so behandelte Scheibe weist infolge der Beschichtung außerdem einen niedrigen elektrischen Widerstand auf, so daß die Scheibe durch Anlegen einer elektrischen Strom quelle beheizbar ist. The thus treated disc also has as a result of the coating on a low electrical resistance, so that the disc by applying an electrical current source is heatable.

Werden derartige Scheiben mit einer weiteren unbeschich teten Scheibe zu Verbundscheiben in Sandwich-Bauweise verarbeitet, eignen sie sich insbesondere für den Einsatz in Kraftfahrzeugen als heizbare Front- oder Heckscheibe mit zusätzlicher Schutzfunktion gegen intensive Sonnen einstrahlung. If such discs with another disc unbeschich ended processed into laminated glass sandwich construction, they are particularly suitable for use in motor vehicles as heatable windshield or rear window with additional protection against irradiation intense sun. Bei derartigen Verbundglasscheiben (VSG- Scheiben) befindet sich - ohne Lufteinschluß - zwischen den zwei dünnen Scheiben aus Mineralglas ein zäh elastische Zwischenlage aus einem Kunststoff (zB Poly vinylbutyrat). In such laminated glass (VSG slices) is located - with no entrapment of air - between the two thin panes of glass, a mineral tough elastic intermediate layer of a plastic material (eg, poly vinyl butyrate). Im Fall der beschichteten Scheibe nach der älteren Patentanmeldung steht die beschichtete Seite in direktem Kontakt mit dem Kunststoff. In the case of the coated pane according to the older patent application, the coated side is in direct contact with the plastic material is. Die Aufgabe der Kunststoffzwischenlage besteht darin, die beiden Scheiben dauerhaft miteinander zu einer stabilen Einheit zu ver binden, die eine deutlich höhere Bruchfestigkeit aufweist als eine einzelne Scheibe. The object of the plastic layer is to bind the two plates are permanently joined to form a stable unit to ver, which has a significantly higher fracture strength than a single disc. Dazu ist eine bestimmte Haftung des Kunststoffes auf der Glas- bzw. Schichtober fläche erforderlich. This requires a certain adhesion of the plastic to the glass or film top surface required.

Weiterhin soll durch die intensive Verbindung des zähen Kunststoffes mit der Glasscheibe im Falle eines Bruches der Scheibe, zB bei einem Unfall, die Bildung und die Ablösung von großen Glassplittern verhindert werden, um Verletzungen so gering wie möglich zu halten. Furthermore, for example, to the intensive connection of the viscous plastic material to the glass pane in the event of breakage of the disc, in an accident, the formation and detachment of large glass fragments are prevented in order to keep as low as possible injury.

Um diese Eigenschaften sicherzustellen, sind für den Einsatz derartiger Verbundscheiben in Kraftfahrzeugen bestimmte Prüfvorschriften erstellt worden und zu erfül len. To ensure these properties, specific test requirements have been created for the use of such laminated glass in motor vehicles and len to fulfillment. Diese Vorschriften und Testmethoden sind in Normen festgehalten. These requirements and test methods are laid down in standards. Bei der Durchführung dieser Prüfungen an VSG-Scheiben, die nach dem in der älteren Patentanmeldung angegebenen Verfahren hergestellt wurden, zeigte sich, daß der Verbund des Schichtsystems nicht ausreicht, da die Glasbruchstücke beim Zerschlagen der Scheibe an der Kunststoff-(Plast)Folie haften sollten. In carrying out these tests in laminated safety glass, which were prepared according to the procedure given in the prior patent application method, it was found that the composite of the layer system is not sufficient, since the glass fragments when dismantling the disc to the plastic (resin) should stick film ,

Der vorliegenden Erfindung liegt deshalb die Aufgabe zugrunde, einen Schichtaufbau zu schaffen, der zu einer wesentlich verbesserten Haftung des Schichtpaketes unter einander führt, ohne die anderen notwendigen physikali schen Daten für die geplante Anwendung zu verschlechtern, insbesondere die hohe Lichttransmission, die elektrische Leitfähigkeit und die Beständigkeit des Schichtpaketes gegenüber dem Biegeprozeß. The present invention therefore has for its object to provide a layer structure, which leads to a substantially improved adhesion of the layer stack with each other without deteriorating the other necessary physi-specific data for the intended application, in particular the high light transmission, electrical conductivity and the resistance of the layer stack over the bending process.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß für die zweite und vierte Schicht eine Legierung aus etwa 80 Gewichtsprozenten Nickel und etwa 20 Gewichtsprozenten Chrom Verwendung findet, wobei man das Substrat mit dem gesamten Schichtpaket auf mindestens die Erweichungs temperatur des Glases erwärmt, in erwärmtem Zustand plastisch verformt und in verformten Zustand abkühlt. This object is inventively achieved in that an alloy of about 80 weight percent nickel and about 20 percent by weight is for the second and fourth layer of chromium use, wherein heating the substrate with the whole layer package to at least the softening temperature of the glass, plastic in the heated state deformed and cooled in the deformed state.

Vorzugsweise werden die zweite und vierte Schicht in einer Dicke aufgebracht, die zu einer größeren Absorption im sichtbaren Bereich führt, als dies dem Endzustand ent spricht, wobei die Temperaturbehandlung in oxidierender Atmosphäre durchgeführt wird, bis die mittlere Transmis sion im sichtbaren Bereich gegenüber derjenigen vor der Temperaturbehandlung um mindestens 5%, vorzugsweise um mindestens 8%, zugenommen hat. Preferably, the second and fourth layers are applied in a thickness which results in a greater absorption in the visible region, as this indicates the final state ent, wherein the temperature treatment is carried out in an oxidizing atmosphere until the average Transmis sion in the visible range compared to that before the temperature treatment, has preferably increased by at least 5% of at least 8%.

Zweckmäßigerweise stellt man den maximalen Transmissions wert im sichtbaren Bereich durch Wahl der Dicke der Schicht zwei, drei und vier vor der Temperaturbehandlung auf 70-80% und erhöht ihn durch die Temperaturbehand lung auf 80-87%. Conveniently, one provides the maximum transmission value in the visible range by selecting the thickness of the layer two, three and four prior to the heat treatment to 70-80%, and increases it by the Temperaturbehand lung to 80-87%.

Mit Vorteil stellt man die Dicke der dritten Schicht (Silber) so ein, daß sich nach der Temperaturbehandlung ein Flächenwiderstand zwischen 2 und 10 Ohm/Quadrat ergibt. Advantageously to set the thickness of the third layer (silver) so that a surface resistance of 2-10 ohms / square resulting after the heat treatment.

Weitere Verfahrensschritte und Merkmale ergeben sich durch die in den Unteransprüchen gekennzeichneten Maßnahmen. Further method steps and features will become apparent by the features characterized in the dependent claims.

Scheiben, die mit der genannten Materialkombination her estellt wurden, zeigen auch nach dem Biegeprozeß eine Haftfestigkeit, die vergleichbar mit den Werten ist, die bei unbeschichteten Scheiben erzielt wurden. Discs, which were estellt with said combination of materials forth show also after the bending process, a bonding strength that is comparable with the values ​​obtained with uncoated glass. Die Zusam mensetzung der gewählten Legierung sollte eingehalten werden, da beispielsweise bei zu hohen Anteilen von Nickel die für eine Windschutzscheibe geforderten Trans missionswerte für sichtbares Licht, die beispielsweise 80 ± 5% beträgt, nicht erreicht werden können oder bei zu hohen Chromanteilen die Temperaturstabilität nicht ausreicht, um die Belastungen des Biegeprozesses ohne Schaden für das Schichtpaket zu überstehen. The together mensetzung the selected alloy should be respected, as for example in excessively high levels of nickel that required for a windshield Trans mission values ​​for visible light, for example, is 80 ± 5% can not be reached or at too high chromium contents is not sufficient temperature stability to survive the stresses of the bending process without damage to the layer packet.

Die Erfindung läßt die verschiedensten Ausführungsmog lichkeiten zu; The invention allows a variety of possibilities to Ausführungsmog; eine davon ist nachstehend anhand einer den Schichtaufbau darstellenden Zeichnung und zweier Diagramme näher beschrieben. one of which is described in more detail below with reference to the layer structure of an illustrative drawing and two graphs.

In Fig. 1 ist mit S das Substrat bezeichnet, das aus einem Mineralglas wie beispielsweise einem übliche Float- Glas wie einem Natrium-Silikat-Glas besteht. In Fig. 1, the substrate is denoted by S, which consists of a mineral glass, such as a conventional float glass such as a sodium silicate glass. Auf dieses Substrat ist eine erste Schicht 1 aus einem Oxid aus der Gruppe Zinnoxid, Siliziumdioxid, Aluminiumoxid, Tantal oxid und Zirkonoxid oder deren Mischoxide aufgebracht. On this substrate 1, a first layer of an oxide from the group tin oxide, silicon dioxide, aluminum oxide, tantalum oxide and zirconium oxide or mixed oxides thereof is deposited. Darauf befindet sich eine zweite Schicht 2 aus etwa 80 Gewichtsprozenten Nickel und etwa 20 Gewichtsprozenten Chrom. Thereafter, a second layer 2 is from about 80 weight percent nickel and about 20 weight percent chromium. Als nächstes folgt eine dritte Schicht 3 aus Sil ber oder einer Silberlegierung mit mindestens 50 Ge wichtsprozent Silberanteil und hierauf wiederum eine vierte Schicht 4 aus etwa 80 Gewichtsprozenten Nickel und etwa 20 Gewichtsprozenten Chrom, und als Abschluß- oder Deckschicht folgt eine fünfte Schicht 5 , die wie die er ste Schicht wiederum aus einem Oxid aus der Gruppe Zinn oxid, Siliziumdioxid, Aluminiumoxid, Tantaloxid und Zir konoxid oder deren Mischoxide besteht. Next follows a third layer 3 of Sil above or a silver alloy with at least 50 Ge weight percent silver content and to this in turn a fourth layer 4 of about 80 weight percent nickel and about 20 weight percent chromium, and as a conclusion or covering layer follows a fifth layer 5, which as it, in turn, composed of an oxide from the group tin oxide, silicon dioxide, aluminum oxide, tantalum oxide and zir konoxid or mixed oxides thereof is. ste layer Es versteht sich, daß im Hinblick auf die dritte Schicht 3 aus Silber kein symmetrischer Schichtaufbau vorliegen muß, sondern daß die Schichtmaterialien innerhalb der in einer Gruppe angegebenen Metalle bzw. Oxide auch variiert werden können. It is understood that there must be no silver layer symmetrical structure with respect to the third layer 3, but that the layer materials can also be varied within the limits specified in a group metals or oxides.

Bei dem in den Diagrammen dargestellten praktischen Aus führungsbeispielen werden in einer Vakuumbeschichtungs anlage für Flachglas, die mit Hochleistungs-Zerstäubungs kathoden (Magnetron-Kathoden) ausgerüstet ist, Glasschei ben aus Float-Glas mit einer Schichtenfolge SnO 2 - NiCr - Ag - NiCr - SnO 2 gemäß Fig. 1 beschichtet, wobei die einzelnen Schichten folgende Dicken aufweisen: Plant for flat glass, the cathode with high-power sputtering (magnetron cathode) are exemplary embodiments, in the illustrated in the diagrams practical off in a vacuum coating provided is glass ticket ben made of float glass with a layer sequence SnO 2 - NiCr - Ag - NiCr - SnO coated 2 of Figure 1, wherein the individual layers have the following thicknesses.:

Die optischen Daten der ungetemperten und getemperten beschichteten Scheiben sind in Fig. 2 dargestellt. The optical data of the unannealed and annealed coated discs are shown in Fig. 2. Diese Scheiben wurden zusammen mit einer unbeschichteten Float- Glasscheibe gleicher Abmessungen in einem Temperofen bei gleichmäßiger Temperaturverteilung einem Biegeprozeß unterzogen, bei dem Spitzentemperaturen von ca. 640°C über einen Zeitraum von etwa 5 Minuten auftreten. These discs were subjected together with an uncoated float glass pane of the same dimensions in an annealing furnace with uniform temperature distribution of a bending process, occurring at the peak temperatures of about 640 ° C over a period of about 5 minutes. Die Lichttransmission der beschichteten Scheibe nach diesem Prozeß beträgt nach dem Erkalten 85%, und der Flächen widerstand zeigt einen Wert von 4,2 Ohm/Quadrat. The light transmission of the coated pane for this process is, after cooling, 85%, and the surface resistance shows a value of 4.2 ohms / square. Danach werden die beiden jeweils zusammengebogenen Scheiben zu VSG-Verbundscheiben weiterverarbeitet, was durch Zwi schenlegen einer Kunststoffolie aus Polyvinylbutyrat und Anwendung eines thermischen Prozesses unter Vakuum erfolgte. Thereafter, the two respectively together bent sheets are further processed to form laminated composite panes, which was carried out by Zvi rule put a plastic film of polyvinyl butyrate and application of a thermal process under vacuum. Werden die resultierenden VSG-Scheiben nun untersucht, dann ergeben sich Werte von 77% für die Lichttransmission und 14% für die Lichtreflexion; If the resulting laminated safety glass now examined, then values ​​result of 77% for light transmission and 14% for light reflection; Werte, die innerhalb der Grenzen liegen, die für eine Zulassung der Scheibe als Automobilfrontscheibe gefordert werden. Values ​​that are within the limits that are required for approval of the disk as an automotive windshield. Gleichzeitig werden bei den Sicherheitsprüfungen nach den einschlägigen Normen (ie Kugelfalltest etc.) die gefor derten Werte erreicht, insbesondere ist dabei die Haftung des beschichteten Glases an der Folie ausreichend, um die Ablösung von größeren Glasbruchstücken zu verhindern. Simultaneously, in the safety tests according to the relevant standards (ie ball drop test, etc.) reaches the Shaped derten values, in particular the adhesion of the coated glass to the sheet is sufficient to prevent detachment of large glass fragments.

Die Haftfestigkeit des Schichtsystems am Glas wurde in Abhängigkeit von der Temperatur getestet. The adhesive strength of the layer system on the glass was tested as a function of temperature. Die Ergebnisse sind in Fig. 3 zu sehen. The results can be seen in Fig. 3. Die Temperzeit beträgt jeweils 10 Minuten. The annealing time is 10 minutes. Die besten Ergebnisse wurden mit NiCr (80/20 Gewichtsprozent) als Schicht 2 und 4 erzielt ( Fig. 3, Kurve 3 ). The best results were achieved with NiCr (80/20 by weight) as layer 2 and 4 (Fig. 3, curve 3). Für dieses Material ist die Haftung unabhängig von der Tempertemperatur. the liability is independent of the annealing temperature for this material. Der ermittelte Wert von ca. 400 kp/cm 2 ist vergleichbar mit der Haftfestigkeit einer Oxidschicht auf Glas. The value of 400 kgf / cm 2 which is comparable with the adhesion of an oxide layer on glass.

Claims (8)

1. Verfahren zum Herstellen von Scheiben mit hohem Transmissionsverhalten im sichtbaren Spektralbereich und mit niedrigem Flächenwiderstand und hohem Refle xionsverhalten für Wärmestrahlung durch Beschichtung von aus Mineralglas bestehenden Substraten mit 1. A method of producing discs having a high transmittance in the visible spectrum and with low area resistance and a high Refle xionsverhalten for thermal radiation by coating consisting of mineral glass substrates with
  • a) einer ersten Schicht aus einem Oxid aus der Gruppe Zinnoxid, Siliziumdioxid, Aluminiumoxid, Tantaloxid und Zirkonoxid oder deren Misch oxide, mit a) a first layer of an oxide from the group tin oxide, silicon dioxide, aluminum oxide, tantalum oxide and zirconium oxide or mixed oxides thereof, with
  • b) einer zweiten Schicht aus Nickel oder einer Legierung mit mindestens 50 Gewichtsprozent Anteil dieses Metalls, mit b) a second layer of nickel or an alloy with at least 50 weight percent of this metal, with
  • c) einer dritten Schicht aus Silber oder einer Silberlegierung mit mindestens 50 Gewichtspro zent Silberanteil, mit c) a third layer of silver or a silver alloy with at least 50 Gewichtspro center silver content, with
  • d) einer vierten Schicht aus Nickel oder aus der die zweite Schicht bildenden Legierung und mit d) a fourth layer of nickel or of the second layer forming alloy and
  • e) einer fünften Schicht aus einem Oxid aus der die erste Gruppe bildenden Oxide, dadurch gekennzeichnet, daß für die zweite und vierte Schicht eine Legierung aus etwa 80 Gewichts prozenten Nickel und etwa 20 Gewichtsprozenten Chrom Verwendung findet, wobei man das Subsrat mit dem gesamten Schichtpaket a) bis 3) auf mindestens die Erweichungstemperatur des Glases erwärmt, in erwärm tem Zustand plastisch verformt und im verformten Zustand abgekühlt. e) a fifth layer comprised of an oxide from the first group of forming oxides, characterized in that for the second and fourth layer an alloy of about 80 weight percent nickel and about 20 weight percent chromium is used to give the Subsrat with the whole layer package a) heated to 3) to at least the softening temperature of the glass is plastically deformed in Warming system state and cooled in the deformed state.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man 2. The method of claim 1, characterized in that
  • a) die Schichten b) und d) in einer Dicke auf bringt, die zu einer größeren Absorption im sichtbaren Bereich führt, als dies dem Endzu stand entspricht und a) the layers b) and d) in a thickness brings which results in a greater absorption in the visible range than was the corresponding Endzu and
  • b) die Temperaturbehandlung in oxidierender Atmos phäre durchführt, bis die mittlere Transmission im sichtbaren Bereich gegenüber derjenigen vor der Temperaturbehandlung um mindestens 5%, vorzugsweise um mindestens 8%, zugenommen hat. b) the heat treatment is carried out in an oxidizing atmos phere until the average transmission in the visible region with respect to that before the heat treatment has at least 5%, preferably at least 8%, increased.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß man den maximalen Transmissionswert im sichtba ren Bereich durch Wahl der Dicke der Schichten b), 3. The method according to claim 2, characterized in that the maximum transmission value in the visible range ren by selecting the thickness of the layers b) one,
  • c) und d) vor der Temperaturbehandlung auf 70-80% einstellt und ihn durch die Temperaturbehandlung auf 80-87% erhöht. c) and d) is adjusted prior to the heat treatment to 70-80%, and increases it by the heat treatment to 80-87%.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Dicke der Schicht c) (Silber) so ein stellt, daß sich nach der Temperaturbehandlung ein Flächenwiderstand zwischen 2 und 10 Ohm/Quadrat ergibt. 4. The method according to claim 1, characterized in that the thickness of the layer c) (Silver) shows such a way that a surface resistance of 2-10 ohms / square resulting after the heat treatment.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die fünfte Schicht e) aus Zinnoxid mit Anteilen von 4 bis 6 Gewichtsprozenten Antimon oder Fluor oder aus Indiumoxid mit 5 bis 15 Gewichtsprozenten Zinn versehen wird. 5. The method according to claim 1, characterized in that the fifth layer e) composed of tin oxide is provided with proportions 4-6 percent by weight antimony or fluoride or of indium oxide with 5 to 15 weight percent tin.
6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die erste a) und die fünfte e) Schicht durch Kathodenzerstäubung von Targets aus den metallischen Oxidbildern in reaktiver Atmosphäre (O 2 und Edelgas) erzeugt und die zweite b), dritte c) und vierte d) Schicht durch Kathodenzerstäubung von Targets aus den genannten Metallen bzw. Metallegierungen in neutraler Atmosphäre (Edelgas). 6. The method according to claim 1, characterized in that the first a) and the fifth e generated) layer by sputtering of targets made of the metallic Oxidbildern (in a reactive atmosphere O 2 and noble gas) and the second b), third c) and fourth d) layers by sputtering of targets made of the said metals or metal alloys in a neutral atmosphere (noble gas).
7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die zweite b) und die vierte d) Schicht aus mindestens einem der genannten Metalle, insbesondere Nickel, erzeugt, das mit mindestens einem metalli schen Zusatz aus der Gruppe 4b, 5b, 6b des periodi schen Systems versetzt ist, wobei der Gesamtzusatz 30 Gewichtsprozente nicht überschreitet. 7. The method according to claim 1, characterized in that one produces the second b) and fourth d) layers of at least one of said metals, in particular nickel, which is consistent with at least one rule metalli additive from the group 4b, 5b, 6b is offset periodi's system wherein the total additive does not exceed 30 percent by weight.
8. Scheibe mit hohem Transmissionsverhalten im sichtba ren Spektralbereich und mit hohem Reflexionsverhal ten für Wärmestrahlung und niedrigem Flächenwider stand, mit einem aus Mineralglas bestehenden Sub strat, mit einer ersten Schicht aus einem Oxid aus der Gruppe Zinnoxid, Siliziumdioxid, Aluminiumoxid, Tantaloxid und Zirkonoxid oder deren Mischoxide, mit einer zweiten Schicht aus etwa 80 Gewichtsteilen Nickel und 20 Gewichtsteilen Chrom, mit einer drit ten Schicht aus Silber oder einer Silberlegierung mit mindestens 50 Gewichtsprozenten Silberanteil, mit einer vierten Schicht aus einer Nickel-Chrom- Legierung und mit einer fünften Schicht aus einem Oxid aus der die erste Gruppe bildenden Oxide, da durch gekennzeichnet, daß die Scheibe gebogen ist. , 8th disc with high transmission characteristics in the visible ren spectral range and with a high Reflexionsverhal th for heat radiation and low surface reflection was strat with a group consisting of mineral glass Sub, with a first layer of an oxide from the group tin oxide, silicon dioxide, aluminum oxide, tantalum oxide and zirconium oxide or their mixed oxides, with a second layer of about 80 parts by weight of nickel and 20 parts by weight of chromium, with a drit th layer of silver or a silver alloy with at least 50 percent by weight silver content, with a fourth layer of a nickel-chromium alloy, and a fifth layer of an oxide from the first group forming oxides, as characterized by, that the disc is curved.
DE3825671A 1987-08-08 1988-07-28 Process for producing panes having a high transmission behaviour in the visible spectral region and a high reflection behaviour for heat radiation, and panes produced by the process Withdrawn DE3825671A1 (en)

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DE4019703A1 (en) * 1990-01-15 1991-07-25 Renker Gmbh & Co Kg Zweigniede Heatable windscreen panel for vehicle - has laminated structure divided horizontally into three areas for high transparency, high sun protection and high heating capacity
DE4026728A1 (en) * 1990-08-24 1992-02-27 Dornier Gmbh Laser protective glazing for visors, industrial glasses, etc. - has transparent IR reflective semiconductor coating
DE4033881A1 (en) * 1990-10-25 1992-04-30 Leybold Ag Sun screen mfr. for vehicles and buildings - by coating glass or translucent plastic substrate with titanium nitride- tin oxide- titanium nitride triple layer
DE4109708C1 (en) * 1991-03-23 1992-11-12 Vegla Vereinigte Glaswerke Gmbh, 5100 Aachen, De
DE4126533A1 (en) * 1991-08-10 1993-02-11 Ver Glaswerke Gmbh A method of contact of the electrically heatable glass panes with transparent heizwiderstandsschichten
DE4135701A1 (en) * 1991-10-30 1993-05-13 Leybold Ag A process for the manufacture of disks with high transmission in the visible spectrum and with high reflection characteristics for thermal radiation, as well as produced by the process slices
DE4139959A1 (en) * 1991-12-04 1993-06-09 Bayerische Motoren Werke Ag, 8000 Muenchen, De Electrically heated, clear flexible sheet, esp. for car rear windows - has layers of thermoplastic, e.g. PET or PVC, with interlayer of conductive metal oxide, pref. indium oxide
DE4211363A1 (en) * 1992-04-04 1993-10-07 Leybold Ag Coating transparent substrate by cathode sputtering - to produce disks of high transmission behaviour in the visible region and giving high reflection to heat radiation
DE4239355A1 (en) * 1992-11-24 1994-05-26 Leybold Ag Transparent substrate with a transparent layer system and method for producing such a layer system
DE4324576C1 (en) * 1993-07-22 1995-01-26 Ver Glaswerke Gmbh Process for producing a multi-layered glass sheet
DE4412318C1 (en) * 1994-04-11 1995-11-16 Ver Glaswerke Gmbh Heat treatment of a provided with a partially reflecting layer of silver glass
DE19520843A1 (en) * 1995-06-08 1996-12-12 Leybold Ag Disc of translucent material as well as process for their preparation
DE19632788A1 (en) * 1996-08-15 1998-02-19 Fraunhofer Ges Forschung Layer system for curved and / or toughened glass panes
DE19807930A1 (en) * 1998-02-25 1999-09-09 Interpane Entw & Beratungsges Highly heat-resistant, heat-reflecting coating
EP1123906A1 (en) 2000-02-02 2001-08-16 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for the production of heat reflecting coating stack for transparent substrates and thus produced coating stack
DE10046810A1 (en) * 2000-02-02 2001-08-16 Fraunhofer Ges Forschung Making heat-reflecting layered coating on glass employs deposition controlled such that functional and blocking layers are merged to form gradient layers
EP1273558A1 (en) 2001-07-02 2003-01-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for the production of a heat reflecting multilayered coating system for a transparent substrate and thus obtained coating
DE10131932C2 (en) * 2000-09-21 2003-09-18 Fraunhofer Ges Forschung A process for producing a heat-reflecting layer system for transparent substrates, and thereafter produced layer system
US6911762B2 (en) 2001-07-26 2005-06-28 Murata Manufacturing Co., Ltd. Surface acoustic wave element, surface acoustic wave device using the same, and method for manufacturing surface acoustic wave element and surface acoustic wave device

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DE4019703A1 (en) * 1990-01-15 1991-07-25 Renker Gmbh & Co Kg Zweigniede Heatable windscreen panel for vehicle - has laminated structure divided horizontally into three areas for high transparency, high sun protection and high heating capacity
DE4026728A1 (en) * 1990-08-24 1992-02-27 Dornier Gmbh Laser protective glazing for visors, industrial glasses, etc. - has transparent IR reflective semiconductor coating
DE4026728C2 (en) * 1990-08-24 2001-05-17 Dornier Gmbh Use of coated transparent viewing windows made of plastic
DE4033881A1 (en) * 1990-10-25 1992-04-30 Leybold Ag Sun screen mfr. for vehicles and buildings - by coating glass or translucent plastic substrate with titanium nitride- tin oxide- titanium nitride triple layer
DE4109708C1 (en) * 1991-03-23 1992-11-12 Vegla Vereinigte Glaswerke Gmbh, 5100 Aachen, De
DE4126533A1 (en) * 1991-08-10 1993-02-11 Ver Glaswerke Gmbh A method of contact of the electrically heatable glass panes with transparent heizwiderstandsschichten
US5299726A (en) * 1991-08-10 1994-04-05 Saint-Gobain Vitrage International "Les Miroirs" Connection for glazings having an electroconductive layer
DE4135701A1 (en) * 1991-10-30 1993-05-13 Leybold Ag A process for the manufacture of disks with high transmission in the visible spectrum and with high reflection characteristics for thermal radiation, as well as produced by the process slices
US5279722A (en) * 1991-10-30 1994-01-18 Leybold Aktiengesellschaft Method for manufacturing panes with high transmissivity in the visible range of the spectrum and with high reflectivity for thermal radiation
DE4139959A1 (en) * 1991-12-04 1993-06-09 Bayerische Motoren Werke Ag, 8000 Muenchen, De Electrically heated, clear flexible sheet, esp. for car rear windows - has layers of thermoplastic, e.g. PET or PVC, with interlayer of conductive metal oxide, pref. indium oxide
DE4211363A1 (en) * 1992-04-04 1993-10-07 Leybold Ag Coating transparent substrate by cathode sputtering - to produce disks of high transmission behaviour in the visible region and giving high reflection to heat radiation
DE4239355A1 (en) * 1992-11-24 1994-05-26 Leybold Ag Transparent substrate with a transparent layer system and method for producing such a layer system
DE4324576C1 (en) * 1993-07-22 1995-01-26 Ver Glaswerke Gmbh Process for producing a multi-layered glass sheet
EP0636587A2 (en) 1993-07-22 1995-02-01 Saint Gobain Vitrage International Process for making a glass pane coated with a multilayer
DE4412318C1 (en) * 1994-04-11 1995-11-16 Ver Glaswerke Gmbh Heat treatment of a provided with a partially reflecting layer of silver glass
DE4412318C2 (en) * 1994-04-11 1998-08-13 Ver Glaswerke Gmbh Heat treatment of a glass plate provided with a partially reflecting layer of silver
DE19520843A1 (en) * 1995-06-08 1996-12-12 Leybold Ag Disc of translucent material as well as process for their preparation
DE19632788A1 (en) * 1996-08-15 1998-02-19 Fraunhofer Ges Forschung Layer system for curved and / or toughened glass panes
DE19807930A1 (en) * 1998-02-25 1999-09-09 Interpane Entw & Beratungsges Highly heat-resistant, heat-reflecting coating
DE19807930B4 (en) * 1998-02-25 2009-04-30 Interpane Entwicklungs- Und Beratungsgesellschaft Mbh & Co.Kg Production of a thermally highly resilient heat-reflecting coating
EP1123906A1 (en) 2000-02-02 2001-08-16 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for the production of heat reflecting coating stack for transparent substrates and thus produced coating stack
DE10046810A1 (en) * 2000-02-02 2001-08-16 Fraunhofer Ges Forschung Making heat-reflecting layered coating on glass employs deposition controlled such that functional and blocking layers are merged to form gradient layers
DE10046810C2 (en) * 2000-02-02 2003-05-28 Fraunhofer Ges Forschung Making heat-reflecting layered coating on glass employs deposition controlled such that functional and blocking layers are merged to form gradient layers
DE10046810C5 (en) * 2000-02-02 2005-10-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for producing a heat-reflecting layer system for transparent substrates and layer system produced therefrom
DE10131932C2 (en) * 2000-09-21 2003-09-18 Fraunhofer Ges Forschung A process for producing a heat-reflecting layer system for transparent substrates, and thereafter produced layer system
EP1273558A1 (en) 2001-07-02 2003-01-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for the production of a heat reflecting multilayered coating system for a transparent substrate and thus obtained coating
US6911762B2 (en) 2001-07-26 2005-06-28 Murata Manufacturing Co., Ltd. Surface acoustic wave element, surface acoustic wave device using the same, and method for manufacturing surface acoustic wave element and surface acoustic wave device
DE10233649B4 (en) * 2001-07-26 2008-09-11 Murata Mfg. Co., Ltd., Nagaokakyo Surface acoustic wave element, surface acoustic wave device using the same, and a method of manufacturing the surface acoustic wave element and the surface acoustic wave device

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